Low molecular weight homo- and copolymers of 1,3-dienes have been known for a long time. It is advantageous for many uses to alter the properties of the hydrophobic polymers in a controlled fashion by the introduction of reactive groups, such as hydroxyl and amine groups. Typically, compounds terminated with these reactive groups may be used as curing agents for epoxy resins, as cross-linking agents or binders for textiles, and as intermediates in the preparation of polyureas, including flexible urethane foams and urethane elastomers. Likewise, polyoxyalkylene polyamines falling within the above description are well known.
For example, U.S. Pat. No. 4,658,062 relates to novel amine terminated polybutadiene compounds of the formula: ##STR1## wherein R is hydrogen, a straight or branched chain alkyl group containing from 1 to 10 carbon atoms or a substituted or unsubstituted aryl or aralkyl group containing one or more benzenoid rings which may be fused or joined by single valency bonds, and n is an integer of from about 5 to about 1500 and a process for the preparation thereof. These materials are made by reacting an alkane or arenesulfonate terminated polybutadiene with a primary amine or ammonia. Further the process involves reacting a polyhydroxybutadiene homopolymer with an alkane or arenesulfonyl chloride or fluoride in the presence of a tertiary amine catalyst at a preferred temperature between 25.degree. and 110.degree. C. The process comprises a two-step procedure including an intermediate alkane or arenesulfonated polybutadiene.
There is described in U.S. Pat. No. 4,721,754 a polybutadiene composition useful for the preparation of polyurea and/or polyurethane elastomers comprising a blend of a polyhydroxybutadiene homopolymer and an amine-terminated polybutadiene. Similarly, U.S. Pat. No. 4,812,524 describes novel polyurea/polyurethane two-component adhesive compositions which comprise the reaction product of (a) a blend of an amine terminated polybutadiene and a polyhydroxybutadiene with (b) an aliphatic or aromatic di- or polyisocyanate and optionally chain extenders, tackifiers, coupling agents fillers and curingly effective amounts of catalysts.
There is U.S. Pat. No. 4,994,621 to Texaco Chemical Company, incorporated by reference herein. This patent teaches that aminated, alkoxylated hydroxyl-terminated polymers can be made by a process involving first polymerizing one or more unsaturated hydrocarbons, such as butadiene, to form a liquid polymer. Next, the liquid polymer is provided with terminal hydroxyl groups. Then, the hydroxylated liquid polymer is alkoxylated with one or more alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, to provide second-ary terminal hydroxyl groups. Finally, the alkoxylated liquid polymer is aminated over a transition metal oxide catalyst, such as a combination of nickel oxide/copper oxide/chromium oxide. If the alkoxylated, hydroxyl-terminated liquid polymer is terminated with primary hydroxyl groups, then the amination does not proceed well. Although it is stated that "Typically, part or all of the double bonds are reduced in this amination procedure", the only structures of the aminated, alkoxylated hydroxyl-terminated polymers presented show the polybutadiene core to be unsaturated. Additionally, it was subsequently found that the end products of the process of this patent retained a relatively high degree of unsaturation.
Further, U.S. patent application Ser. No. 07/787,199, incorporated by reference herein, describes the synthesis of novel amine derivatives of hydroxyl-terminated polybutadienes having the formula: ##STR2## where x and y are integers, formed by amination and hydrogenation of a hydroxyl-terminated polybutadiene oligomer having an average molecular weight of 100 to 20,000 and a hydroxyl content of 0.1 to 20 meq/g in the presence of an inert solvent over a catalyst comprising Ni-Cu-Cr supported on alumina at a partial pressure of hydrogen sufficient to allow a flow rate of about 1 to 1000 scf H.sub.2 /lb hydroxyl-terminated polybutadiene (HTPB).
The term hydroxyl-terminated polybutadienes (HTPB) is used herein to include hydroxyl-terminated copolymers where at least one of the monomers used is butadiene. This definition includes hydroxyl-terminated homopolymers of butadiene.
It is always desirable to produce polyamines with improved properties for specific uses. It would be desirable to produce aliphatic amine derivatives of alkoxylated polybutadienes terminated with secondary hydroxyl groups which possessed a high concentration of secondary alkyl primary amines along with a high degree of saturation and a low equivalent weight of primary alkyl primary amines or secondary amines. Such compositions would be expected to be useful in RIM and polyurethane applications.